Metal-containing azo dyestuffs



United States Patent C METAL-CONTAENHNG AZO DYESTUFFS Reinhard Neier,Basel, and Charles Petitiean and Walter Wellrli, Riehen, Switzerland,assignors, by mesne assignments, to Saul & C0,, Newark, N. L, as nomineeof Fidelity Union Trust Company, executive trustee under Sandoz Trust NoDrawing. Application January 18, 1954 Serial No. 404,811

Claims priority, application Switzerland September 4, 1951 6 Claims.(Cl. 260-448) The present application is a continuation-in-part of thecopending application Serial No. 304,012, filed August 12, 1952, nowPatent No. 2,779,758, and relates to new metal-containing azo dyestuifs.

A primary object of the invention is the embodiment of metal-containingazo dyestuffs of especial utility in the dyeing of Wool, silk, leatherand artificial nitrogencontaining fibers such as synthetic polyamidefibers (e. g. nylon, Perlon, etc.), from neutral to weakly aciddyebaths. This object is realized by the dyestufis according to theinvention which correspond in their metalfree state to the formula RN==Nazo-R-:r

J wherein the nucleus I may bear further substituents, e. g. alkylgroups, R stands for the radical of a diazo comand sulfonamide groups,and with a cobalt atom when x denotes at least one group selected fromsulfonic acid, carboxylic acid, acylamino, alkylsulfonyl and sulfonamidegroups.

A preferred series of the metal-containing azo dyestuits in accordancewith the invention possess the formula J2 2) wherein R, x and I have theabove mentioned significances, R"O stands for the radical of a couplingcomponent of the hydroxybenzene, hydroxynaphthalene, 5-pyrazolone,acetoacetylaminoalkane, acetoacetylaminobenzene oracetoacetylaminonaphthalene series, and Me standswhen x denotes at leastone group selected from carboxylic acid, acylamino, alkylsuifonyl andsulfonamide groupsfor a chromium atom, andwhen x denotes at least onegroup selected from sulfonic acid, carboxylic acid, acylamino,alkylsulfonyl and sulfonamide groups-- for a cobalt atom.

The new dyestuffs are prepared by treating disazo compounds as obtainedinter alia according to the process of the copending application SerialNo. 304,012 and which correspond to the Formula 1, with chromiumyieldingagents when x denotes at least one group selected from carboxylic acid,acylamino, alkylsulfonyl and sulfonamide groups, and withcobalt-yielding agents when x denotes at least one group selected fromsulfonic acid, carboxylic acid, acylamino, alkylsulfonyl and sulfonamidegroups. a

In carrying out the process a preferred method consists in using for themetallization of two molecules of disazo compound less than one atom ofchromium, e. g. 0.5 'to 0.7 atom, to yield for example the so-called1:2-complex compounds wherein about one atom of metal is present for twomolecules of disazo compound.

The aforesaid disazo compounds may be obtained, for example, by couplingone mol of the diazo compound of a monoazo dyestuff of the formulawherein R and I have the precedingly-recited significances, with one molof a corresponding coupling component of the formula H-R 4 wherein hasthe precedingly-recited significance, or by coupling one mol of thediazo compound of an amine of the benzene or naphthalene series with onemol of a monoazo dyestufi of the formula azoR 5 wherelu OH I all and Ihave the precedingly-recited significances. The monoazo dyestufi ofFormula 3 may be prepared by coupling a diazotized amine of the benzeneseries with a 1-hydroxy-2-N-acylaminobenzene and then converting theacylamino group of the coupling product into the NH,, group bysaponification, or by reducing the nitro group of a compound of theformula component which couples-in orthoposition to the hydroxy group.

The expression sulfonamide groups comprises not only the simple --SO .NHgroup but also sulfonamide groups which are substituted by alkyl,aralkyl, cycloalkyl or aryl at the nitrogen atom. Particularlyinteresting representatives of these groups are the sulfonic acidmethylamide, the sulfonic acid-(2'-hydroxy)-ethylamide, the sulfonicacid-(3-methoxy)-propylamide and the sulfonicacid-(2-carboxy)-phenylamide groups.

The conversion of the disazo compounds into the cobalt-containing orchromium-containing azo dyest-ufi's is advantageously carried out atelevated temperature in aqueous solution or suspension or in organicmedium, e. g.

in formamide, or in a molten alkali metal salt of a low J molecularaliphatic monocarboxylic acid, with the aid of a cobaltorchromium-yielding agent. These agents comprise, for example, salts ofbivalent cobalt, such as cobalt sulfate, cobalt formate and cobaltacetate, and salts of trivalent chromium such as chromium fluoride,chromium sulfate, chromium acetate and potassium chromium sulfate. Thealkali metal chromates and bichromates are also excellently suitable forthe metallization. If the metallization is carried out in a moltenalkali metal salt of a low molecular aliphatic monocarboxylic acid,insoluble metal compounds, such as cobalt hydroxide or cobalt carbonate,may also be employed.

The metallization products are advantageously precipitated from thereaction solution by the addition of salt (sodium chloride) after whichthey are filtered off and finally dried. They are generally dark powderswhich dissolve in water with yellow, orange, brown, red, violet, blue,olive to gray coloration, and dye wool, silk, nitrogenous syntheticfibers such as synthetic polyamide fibers and leather from a neutral toweakly acid bath in similar shades which are characterized by excellentfastness properties.

The following examples further illustrate the invention by means ofrepresentative embodiments thereof; however, it is not intended torestrict the invention to the said examples. In the latter, the parts'are parts by weight, the percentages are percentages by weight, and thetemperatures are in degrees centigrade.

In connection with the nomenclature of the monoazo compounds serving forthe preparation of the starting products in the examples, it may benoted that in all cases where two benzene nuclei are linked together bythe azo group, the monoazo compound is defined as a. 1,1-azobenzenecompound, whereas in those cases where a benzene nucleus is connected toa naphthalene nucleus by the azo group, the monoazo compound is definedas a "benzene-azo-naphthalene compound.

EXAMPLE 1 and is a brown powder which dyes wool, silk, syntheticpolyamide fibers and leather from a neutral to weakly acid bath inorange shades of good fastness to light and very good fastness towashing, to fulling and to potting.

EXAMPLE 2 formula N=N C Ol HOsS and, in the dried state, is a darkpowder which dyes wool, silk, synthetic polyamide fibers and leatherfrom a neutral to weakly acid bath in reddish brown shades of excellentfastness to light, to washing, to fulling and to potting.

EXAMPLE 3 49.8 parts of the disazo compound, obtained by couplingdiazotized l-(3-amino-4-hydroxy)benzene-azo naphthalene with2-hydroxynaphthalene-7-sulfonic acid, are dissolved together with 4parts of sodium hydroxide in 2000 parts of water at Into the resultantsolution, at 60 and while stirring thoroughly, there is added dropwise amixture of 14.2 parts of crystalline cobaltous sulfate, parts of aqueoustartaric acid solution. of 3% strength and 18.4 parts of aqueous sodiumhydroxide solution of 30% strength. After stirring for ahalf hour, thecobalt complex compound is precipitated from the reaction mixture by theaddition of sodium chloride after which it is filtered off and dried. Itcorresponds to the II N formula HOaS- and is a dark powder which dyesWool, silk, synthetic polyamide fibers and leather from a neutral toweakly acid bath in reddish brown shades of noteworthy fastness tolight, to washing, to fulling and to potting.

EXAMPLE 4 withdrawn from the reaction mixture. After the addition ofsodium chloride to the cobaltizing solution, the resultant cobaltcomplex compound is filtered off and then dried. It is identical withthe cobalt-containing azo dyestufi obtained according to Example 3.

EXAMPLE 29.5 parts of the disazo dyestulf obtained by coupling3-amino-4-hydroxy-l,1-azobenzene-3-sulfonic acid-(2"-hydroxy)-ethylamide with1-carbo-(2'-ethoxy)-ethoxyamino-7-hydroxynaphthalene, are refluxed inaqueous solution together with 16.1 parts of the sodium salt of 1-hydroxy-benzene-Z-carboxy1ic acid, containing 8.1% of chromium incomplex combination, until the disazo compound has been converted intothe chromium-containing azo dyestuff. The latter is precipitated fromthe reaction solution by the addition of sodium chloride, after which itis filtered oif, dried and ground. It corresponds to the formula and isa dark powder which dyes wool, silk, synthetic polyamide fibers andleather from a neutral to weakly acid bath in grayish olive shades ofvery good fastness to light, to washing, to fulling and to potting.

EXAMPLE 6 44.7 parts of the disazo compound, obtained by couplingdiazotized 3-amino-4-hydroxy-1,1-azobenzene-3'- sulfonic acid amide with2-hydroxynaphthalene, are heated to 125 for approximately one hour in200 parts of formamide together with 28 parts of potassium chromium(III) sulfate, while stirring. The resultant chromium complex compoundis precipitated by diluting the chroming mixture with concentratedaqueous sodium chloride solution, after which it is filtered off anddried. It corresponds to the formula S Oz N I'm, 1% a and is a darkpowder which dyes wool, silk, synthetic polyamide fibers and leatherfrom a neutral to weakly acid bath in gray-brown shades of good fastnessproperties.

The following table sets forth additional metal-containing azo dyestuffsaccording to the present invention. The cobalt complex compounds can beprepared according to one of the methods set forth in Examples 1 to 4and the chromium complex compounds can be prepared according to one ofthe methods described in Examples 5 and 6. In the table, themetal-containing azo dyestuffs are characterized in column If by themetal-free disazo compounds from which they are derived, in column IIIby the metal which the azo dyestuffs contain in complex combination, andin column IV by the shade of the dye- (II) (III) (IV) Example No.

7 3 amino 4 hydroxy 1,1 azobenzene- Co orange.

4-sulfonic acid acetoacetylaminobenzene.

8 1 (3' amino 4 hydroxy) benzene C0 reddishazonaphthalene 5 sulionicacid brown. 2-hydroxynaphthalene.

9 3 amino 4 hydroxy -1,1 azobenzene Go brown.

-- 2 hydroxynaphthalene 4 sulionic acid.

10 3-amino-4-hydroxy-4-methyl-1,1- 00 red- 1 azobenzene 1hydroxynaphbrown.

thalene-4-sulfonic acid.

11 3 amino 4 hydroxy -1,1 azobenzene- 3 Go Do.

4'-sulfonic acid Z-hydroxynaphthalene.

12 1 (3 amino 4-hydroxy) benzene C0 D0.

azonaphthalene 4 sulfonic acid 2-liydroxynaphthalene.

13 2 (3 amino 4 hydroxy) benzene Go Do,

azonaphthalene 6 sulfouic acid 2-hydroxynaphthalene.

14 3 amino 4 a hydroxy -1,1 azobenzene C0 Do,

- 2 hydroxynaphthaiene 6 sulfonic acid.

15 1 (3 amino 4' hydroxy) benzene C0 azonaphthaiene 4 sulfonic acid lil-acetylamino-7-hydroxynaphthalene.

15 3 amino 4 hydroxy 1,1 azobenzene- D 2'-carboxylic acidi-propionylamino-7-hydroxynaphthalene.

17 3 amino 4 hydroxy 1,1 azobenzene- G D 3-sulfonic acid amide 1-carbo-(2-ethoxy)-ethoxyamino 7 hydroxynaphthalene. I

13 1 (3 amino 4 hydroxy) benzene C d.

azonaphthalene 4 sulfonic acid br w l-phenyl-B-methyhdpyrazoione.

19 1- (3-amino-4-hydroxy) -benzene-azo- D naphthalene 5 sullonie acid 1(3' chioro) phenyl 3 methyl 5 pyrazoione.

20 1 (2 hydroxy 3 amino 5-methyl) 3 bl benzene azo naphthalene 5sniionic gra,y

acid 2-hydroxynaphthalene.

21 1- (2'-hydr0xy-3-amino-5-tert.butyl) C D benzene azo -naphthalene 5sulionic acid 2-hydroxynaphthalenc.

22 3 amino 4 hydroxy 1,1 azobenzene CO bor- 4-sulfonic acid amide1,3-di- (1 hydroxy-benzene.

23 3 amino 4 hydroxy -1,1' azobenzene (3 d.

3-sulfonic acid amide Z-hybr w droxynaphthalene.

24 2 hydroxy 3 amino 5 methyl-1,1- O b azo benzene 3 sulionie acid amidegray, 2-hydroxynaphthaien".

25 3 amino 4 hydroxy 1,1 azobenzene- O r 3-sult'onie acid amideacetoacetylaminobenzene.

26 3 am ino 4 hydroxy 1,1 azobenzene- (3 D 3-sulfonic acid-(2-hydroxv)-ethylamide acetoacetylaminobenzone.

27 3 amino 4 hydroxy i.1- aznbenzene C gray- 4-suli'onicacid-(2"-hydroxy)'cthy1aliv mide l-carbo-(2-ethoxy)-ethoxyamino-7-hydroxynaphthalene.

28 3 amino 4 hydroxy i, iazcbenzene- C D 4-sulfonic acid amide l-carb0(2 ethoxy) ethoxyamino 7 hydroxynaphthalene.

29 2 (3 amino 4' hydroxy) benzene 00 redazo-naphthalene-l-sulionic acidbrown z hydroxynaphthalene.

30 3 amino 4 hydroxy 4 ethoxy 1,1- G 1) azobenzene2-hydroxynaphthalene-7-sulfonic acid.

31 3-amino 4 -hydroxy -4 -methoxy 1,1 Co orange.

azobenzene l-acetoaeetylaminobenzene-4-sulfonie acid.

32 8-amino4-hydroxy-2,4-dimethyl-1,1- 00 red.

azobenzone-6-sulionic acid 2- brown. hydroxynaphthalene.

33 3 amino 4 hydroxy 2 methyl 3 00 Do. ciiloro 1,1 azobenzene 5 sulfonicacid 2-hydroxynaphthalene.

34 3-amino-4-hydroxy-2,4,6 -trirnethyl C0 D0.

1,1-azobenzene 2-hydroxynaphthalene-Wsnlfonic acid.

35 S-amino -4-hydr0xy -4' tertamyl -1,l- C0 D0.

azobenzene Z-hydroxynaphthalene-fi-sulfonic acid.

36 3 amino 4 hydroxy 4 nitro 1,1- 00 brown.

azobenzene 2-hydroxynaphthalene-4-sulionic acid.

37 3 4 amino 4 hydroxy 3 mothylsulfo- Cr brownn3 l-l ,V-azobenzeneZ-hydroxygray.

naphthalene-tsuiionic acid amide.

ings of the corresponding metal complex compounds on wool.

Table i e metal-containing azo dyestutfs corresponding to one of (I) theformulae (II) (III) (IV) Example RN=N 383-amino-4-hydroxy-1.l-azobenzene- Or Brown- 3'-sulfonioacid-(2"-hydroxyl-ethylagray. t! or mide 2-hydroxynaphthalene. N

39 3 amino 4 hydroxy 1,l-azobenzene- Cr olive. L

sulifinieaeid 1amide hl-dcarb0- I 2 -e oxy -et oxyamino-7- yroxynaphthalene. 10

40 3 amino 4 hydroxy 1,1-azobenzene- Cr orange- 2 4-sulionic acid amider 1,3- brown. nd dihydroxy-benzene a 41B-amino-4-hydroxy-1,1-azobenzene- Or orange.

3-sulfonic acid amide l-phenyl-3-methyl-5-pyraz0lone.

42 3-amino-4-hydroxy-3-methylsulfonyl- Cr yellow- 1,1-azobenzeneacetoacetylbrown. amino-benzene.

43" 2 hydroxy 3 amino 5 methyl 1,1- Cr bluer- 1/ N Goazobenzene-3-sulfonic acid amide g y. H Z-hydroxynaphthale'rie. N

44 2 hydroxy- 3 amino '5 --methyl 1;1- C1 g ee s azobenzene-2-carboxylieacid gray.

acetylamino -'7 hydroxynaphtha- 2 ene.

4s 3- 1 1n 1;y 1 r o y-1.1'a l e Cr wherein R stands for a memberselected from the group 46 3 amino-7-hytlilrorynaphthalmi; 0 consistingof the radicals of diazo components of the insummic brown benzene andnaphthalene series, R O stands fora mide 2-'hydroxynaphthalene." Vmember selected from the group consisting of the radi- 47 52 33 12 6ggffgflfig xigggfig fg: olive cals of coupling components of thehydroxybenzene,

ng de g-carbo-(I;.1%tlio1iy)- hydroxynaphthalene, 5 pyrazolone,acetoace'tylaminoe oxyaminoy roxynap a one. l

48 3 amino 4, .hydmxvy lflhambmzeney Cr mama alkane,acetoacetylaminobenzene and acetoacetylamino 4' -s u1ror3 c acid amidle1-phen--' naphthalene series, x stands for at least one group sey -me y-5-pyrazo one. I

49 2,hYdmxY .3 'amn0 5 methy1pun blue, lected from the class consistingof the carboxylic acid, azlobgnzenet iiglfolriicacid amld0grayacylamrno, methylsulfonyl and sulfonamide groups, x 2- y roxynapaene. a

50 3 amino 4 hydmxy Lluazobemena Cr ohm stands for at least one groupselected tromthc class con- 3- sul,fonicacid amide 1-carbo--- sisting ofthe sulfon1c'ac1d, carboxylic acid, acylamlno, g gg fggtggjinethylsulfo'nyl and 'sulfonamide groups, and y stands for 51 -s3-ambino-4 gydrgx 2-{g h9 1,1- Or Do. a member selected from the groupconsisting of hydroazo enzene- -su onicac arm e a l carbo (2, ethoxy)ethoxyammo 7 gen and lovue r alkyl, and wherem each -O atom 1s 52 3 a iiri li ri i ri ll' a obenzene 00 yellow m Ortho poslt1on to an N=Ngroup' 4. O- I Z h i; Lacetoacety}- brown 2.hTlf1e collaalt-contalningazo dyestufi corresponding aminonap t a ene. to t e rmu 533-amino-4-hydroxy-1,1-azobenzene- C0 Do. 0 a

4-s;1l{0nieacgdamide l-acetoace yamino ntane.

54 1 (3 amino 4 hydroxy) benzene C0 D0. H038 N N Oazonaphthalenel-sullonic acid I l-acetoacetylaminooctane. N

55 1 (3 amino 4 hydroxy) benzene Cr orange- H azonaphthalenel-sulfonicacid brown. N 1 (5.6',7.8 tetrahydro) naphthyl I(2)-3-methyl-5-pyrazolone. CO

?-0 CH EXAMPLE 56 3 In a porcelain container of a capacity of about 2liters, a solution is prepared which c'o'ntains'0.5 part of thechromium-containing azo dyestuft according to Example v 5 and 0.5 partof concentrated acetic acid in 500 parts s.. O of water at 40. SO'partsof thoroughly pre-wetted wool I are introduced into the'thus-prepareddyebath. The tem- I perature of the bath is raised to 100 in the courseof 30 All minutes, while repeatedly moving the material about therein,and the temperature is then maintained at 100? for one hour. At theendof this time, the dyestuff has completely been drawn onto the fiber. Thedyed mateml is thoroughly rinsed in Wale! and then dried- It is 4. Thecobalt-containing azo dyestufi corresponding to dyed in an olive shadeof excellent fastness to light, to t formula washing, to fulling andtopotting. Y

Synthetic polyatnide fiber and silk can be'dyed in simijf l\ L\I O lar.manner, and with these materials the dyeing process 1;

can be carried out below the boiling temperature. Simi- 0 i lar perfectdyeings can also be obtained uponwool, em l ploying a maximumtemperature of about 90, H03s' 0- -Having thus disclosed the inventionwhatis claimedis:

1. A member selected from the class consisting of 2 3. Thecobalt-containing azo dyestuff corresponding to the formula 5. Thechromium-containing azo dycstufi corrcspond- 6. The chromium-contain ixg azo dyestufl corresponding to the formula ing to the formula N:mciolmzi N 5 sio, N i

I g NH,

Reterences Cited in thc file of this patent 15 UNITED STATES PATENTS1,947,027 Woodward Feb. 13, 1934 2,735,844 Neier Feb. 21, 1956

1. A MEMBER SELECTED FROM THE CLASS CONSISTING OF METAL-CONTAINING AZODYESTUFFS CORRESPONDING TO ONE OF THE FORMULAE